PRODUCTS & MARKETS

ETHYLENE


MONOMERS



Ethylene (IUPAC name: ethene) is a gaseous organic compound with the formula C2H4. It is the simplest alkene (older name: olefin from its oil-forming property). Because it contains a carbon-carbon double bond, ethylene is classified as an unsaturated hydrocarbon. Ethylene is widely used in industry and also has a role in biology as a hormone. Ethylene is the most produced organic compound in the world; global production of ethylene exceeded 107 million metric tonnes in 2005. To meet the ever increasing demand for ethylene, sharp increases in production facilities have been added globally, particularly in the Persian Gulf countries.

Structure and bonding
This hydrocarbon has four hydrogen atoms bound to a pair of carbon atoms that are connected by a double bond. All six atoms that comprise ethylene are coplanar. The H-C-H angle is 119°, close to the 120° for ideal sp² hybridized carbon. The molecule is also relatively rigid: rotation about the C-C bond is a high energy process that requires breaking the π-bond.

Uses
Major industrial reactions of ethylene include in order of scale: 1) polymerization, 2) oxidation, 3) halogenation and hydrohalogenation, 4) alkylation, 5) hydration, 6) oligomerization, and 7) hydroformylation. Ethylene can also be hydrated to give ethanol, but this method is rarely used industrially. In the United States and Europe, approximately 90% of ethylene is used to produce three chemical compounds—ethylene oxide, ethylene dichloride, and ethylbenzene—and a variety of kinds of polyethylene.
Main industrial uses of ethylene. Clockwise from the upper right: its conversions to ethylene oxide, precursor to ethylene glycol, to ethylbenzene, precursor to styrene, to various kinds of polyethylene, to ethylene dichloride, precursor to vinyl chloride.

Polymerization
Polyethylenes of various types consume more than half of world ethylene supply. Polyethylene, also called polythene, is the world's most widely-used plastic, being primarily used to make films used in packaging, carrier bags and trash liners. Linear alpha-olefins, produced by oligomerization (formation of short polymers) are used as precursorsdetergents, plasticisers, synthetic lubricants and additives, but also as co-monomers in the production of polyethylenes.

Oxidation
Ethylene is oxidized to produce ethylene oxide, a key raw material in the production of surfactants and detergents by ethoxylation. Ethylene oxide also hydrolyzed to produce ethylene glycol, widely used as an automotive antifreeze as well as higher molecular weight glycols and glycol ethers.
Ethylene undergoes oxidation by palladium to give acetaldehyde. This conversion remains a major industrial process (10M kg/y). The process proceeds via the initial complexation of ethylene to a Pd(II) center.

Halogenation and hydrohalogenation
Major intermediates from the halogenation and hydrohalogenation of ethylene include ethylene dichloride, ethyl chloride and ethylene dibromide. The addition of chlorine entails "oxychlorination," i.e. chlorine itself is not used. Some products derived from this group are polyvinyl chloride, trichloroethylene, perchloroethylene, methyl chloroform, polyvinylidiene chloride and copolymers, and ethyl bromide.

Alkylation
Major chemical intermediates from the alkylation with ethylene is ethylbenzene, precursor to styrene. Styrene is used principally in polystyrene for packaging and insulation, as well as in styrene-butadiene rubber for tires and footwear. On a smaller scale, ethyltoluene, ethylanilines, 1,4-hexadiene, and aluminium alkyls. Products of these intermediates include polystyrene, unsaturated polyesters and ethylene-propylene terpolymers.

Oxo-reaction
The hydroformylation (oxo-reaction) of ethylene results in propionaldehyde, a precursor to propionic acid and n-propyl alcohol.

Niche uses
Given the scale of its production, ethylene is inevitably used in thousands of applications. For example, ethylene is an anesthetic agent (in an 85% ethylene/15% oxygen ratio). It can also be used to hasten fruit ripening, as well as a welding gas.

Production
Ethylene is produced in the petrochemical industry by steam cracking. In this process, gaseous or light liquid hydrocarbons are heated to 750–950 °C, inducing numerous free radical reactions followed by immediate quench to stop these reactions. This process converts large hydrocarbons into smaller ones and introduces unsaturation. Ethylene is separated from the resulting complex mixture by repeated compression and distillation. In a related process used in oil refineries, high molecular weight hydrocarbons are cracked over zeolite catalysts. Heavier feedstocks, such as naphtha and gas oils require at least two "quench towers" downstream of the cracking furnaces to recirculate pyrolysis-derived gasoline and process water. When cracking a mixture of ethane and propane, only one water quench tower is required.

The areas of an ethylene plant are:
1. steam cracking furnaces:
2. primary and secondary heat recovery with quench;
3. a dilution steam recycle system between the furnaces and the quench system;
4. primary compression of the cracked gas (3 stages of compression);
5. hydrogen sulfide and carbon dioxide removal (acid gas removal);
6. secondary compression (1 or 2 stages);
7. drying of the cracked gas;
8. cryogenic treatment;
9. all of the cold cracked gas stream goes to the demethanizer tower. The overhead stream from the demethanizer tower consists of all the hydrogen and methane that was in the cracked gas stream. Cryogenically (−250 °F (−156.7 °C)) treating this overhead stream separates hydrogen from methane. Methane recovery is critical to the economical operation of an ethylene plant.
10. the bottom stream from the demethanizer tower goes to the deethanizer tower. The overhead stream from the deethanizer tower consists of all the C2,'s that were in the cracked gas stream. The C2 stream contains acetylene, which is explosive above 200 kPa (29 psi). If the partial pressure of acetylene is expected to exceed these values, the C2 stream is partially hydrogenated. The C2's then proceed to a C2 splitter. The product ethylene is taken from the overhead of the tower and the ethane coming from the bottom of the splitter is recycled to the furnaces to be cracked again;
11. the bottom stream from the de-ethanizer tower goes to the depropanizer tower. The overhead stream from the depropanizer tower consists of all the C3's that were in the cracked gas stream. Before feeding the C3's to the C3 splitter, the stream is hydrogenated to convert the methylacetylene and propadiene (allene) mix. This stream is then sent to the C3 splitter. The overhead stream from the C3 splitter is product propylene and the bottom stream is propane which is sent back to the furnaces for cracking or used as fuel.
12. The bottom stream from the depropanizer tower is fed to the debutanizer tower. The overhead stream from the debutanizer is all of the C4's that were in the cracked gas stream. The bottom stream from the debutanizer (light pyrolysis gasoline) consists of everything in the cracked gas stream that is C5 or heavier.

Since ethylene production is energy intensive, much effort has been dedicated to recovering heat from the gas leaving the furnaces. Most of the energy recovered from the cracked gas is used to make high pressure (1200 psig) steam. This steam is in turn used to drive the turbines for compressing cracked gas, the propylene refrigeration compressor, and the ethylene refrigeration compressor. An ethylene plant, once running, does not need to import steam to drive its steam turbines. A typical world scale ethylene plant (about 1.5 billion pounds of ethylene per year) uses a 45,000 horsepower (34,000 kW) cracked gas compressor, a 30,000 horsepower (22,000 kW) propylene compressor, and a 15,000 horsepower (11,000 kW) ethylene compressor.

Laboratory aspects
Ethylene can be produced in the laboratory by heating absolute ethanol with concentrated sulfuric acid. Interestingly for such a useful compound, ethylene is rarely used in organic synthesis in the laboratory.
Being a simple molecule, ethylene is spectroscopically simple. Its UV-vis spectrum is still used as a test of theoretical methods.

History
Ethylene appears to have been discovered by Johann Joachim Becher, who obtained it by heating ethanol with sulfuric acid; he mentioned the gas in his Physica Subterranea (1669). Joseph Priestley also mentions the gas in his Experiments and observations relating to the various branches of natural philosophy: with a continuation of the observations on air (1779), where he reports that Jan Ingenhousz saw ethylene synthesized in the same way by a Mr. Enée in Amsterdam in 1777 and that Ingenhousz subsequently produced the gas himself. The properties of ethylene were studied in 1795 by four Dutch chemists, Johann Rudolph Deimann, Adrien Paets van Troostwyck, Anthoni Lauwerenburgh and Nicolas Bondt, who found that it differed from hydrogen gas and that it contained both carbon and hydrogen. This group also discovered that ethylene could be combined with chlorine to produce the oil of the Dutch chemists, 1,2-dichloroethane; this discovery gave ethylene the name used for it at that time, olefiant gas (oil-making gas.)
In the mid-19th century, the suffix -ene (an Ancient Greek root added to the end of female names meaning "daughter of") was widely used to refer to a molecule or part thereof that contained one fewer hydrogen atoms than the molecule being modified. Thus, ethylene (C2H4) was the "daughter of ethyl" (C2H5). The name ethylene was used in this sense as early as 1852.
In 1866, the German chemist August Wilhelm von Hofmann proposed a system of hydrocarbon nomenclature in which the suffixes -ane, -ene, -ine, -one, and -une were used to denote the hydrocarbons with 0, 2, 4, 6, and 8 fewer hydrogens than their parent alkane. In this system, ethylene became ethene. Hofmann's system eventually became the basis for the Geneva nomenclature approved by the International Congress of Chemists in 1892, which remains at the core of the IUPAC nomenclature. However, by that time, the name ethylene was deeply entrenched, and it remains in wide use today, especially in the chemical industry.

Nomenclature
The 1979 IUPAC nomenclature rules made an exception for retaining the non-systematic name ethylene, however, this decision was reversed in the 1993 rules so the IUPAC name is now ethene.

Safety
Like all hydrocarbons, ethylene is an asphyxiant and combustable. It has been used as an anesthetic.



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